WO2013155652A1 - 一种聚氨酯分散剂及其制备方法 - Google Patents

一种聚氨酯分散剂及其制备方法 Download PDF

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Publication number
WO2013155652A1
WO2013155652A1 PCT/CN2012/001356 CN2012001356W WO2013155652A1 WO 2013155652 A1 WO2013155652 A1 WO 2013155652A1 CN 2012001356 W CN2012001356 W CN 2012001356W WO 2013155652 A1 WO2013155652 A1 WO 2013155652A1
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Prior art keywords
component
compound
anhydride
group
nitrogen
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PCT/CN2012/001356
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English (en)
French (fr)
Inventor
王志军
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Wang Zhijun
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Publication date
Application filed by Wang Zhijun filed Critical Wang Zhijun
Priority to US14/394,741 priority Critical patent/US9670305B2/en
Priority to EP12874369.7A priority patent/EP2839873B1/en
Priority to JP2015504831A priority patent/JP5960343B2/ja
Priority to KR1020147032126A priority patent/KR101644497B1/ko
Publication of WO2013155652A1 publication Critical patent/WO2013155652A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/285—Nitrogen containing compounds
    • C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7875—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/7887—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring having two nitrogen atoms in the ring
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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/795—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of mixtures of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates with aromatic isocyanates or isothiocyanates
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    • C09D11/00—Inks
    • C09D11/02—Printing inks
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Definitions

  • the present invention relates to a polyurethane type dispersant which is reacted with a hydroxy compound by an isocyanate polymer after being reacted with a hydroxy compound, and finally terminated with a self-made novel anchoring end group.
  • the present invention further illustrates the preparation of such novel anchoring end groups and their use in polyurethane dispersants.
  • a dispersant is a surfactant having both opposite properties of lipophilicity and hydrophilicity in a molecule, and a part of its structure has a highly polar anchoring end group, which is easily adsorbed on the surface of the solid particles, and One part is a less polar solvated long molecular chain with good affinity to the dispersion medium (resin or solvent). Therefore, the dispersant can uniformly disperse solid particles of inorganic, organic pigments which are hardly soluble in liquid, and at the same time prevent sedimentation and aggregation of solid particles to form a relatively stable suspension.
  • high molecular weight dispersants are an essential additive, such as polyacrylates, Polyurethane dispersant, etc.
  • polyurethane dispersants can easily obtain organic pigments due to their special polyisocyanate cores and their high reactivity of NCO, which can react with different polar monohydric alcohol tails to form sterically hindered segments.
  • the high stability and high molecular weight dispersant with wide compatibility with the system makes the dispersion stability of many high performance organic pigments no longer a problem.
  • No. 4,032,698 teaches a polyurethane-based dispersant prepared from 2.5-6 functional polyisocyanates, polyacrylate monols and anchored end groups, anchored end groups containing -SH or -OH or -NH 2
  • An alkaline reactant such as a reactive group such as dicyandiamide, dinitroaniline, diaminomaleonitrile, 3-amino-1, 2, 3-triazole, and the like.
  • EP 154 678 mentions a polyurethane-based dispersant prepared from polyisocyanates, hydroxy compounds and a compound containing zerewitinoff active hydrogen and at least one nitrogen-containing basic group.
  • the active hydrogen-containing compound as the anchoring terminal group preferably employs a -NH(containing heterocyclic compound such as 1-(2-aminoethyl)piperazine, 3-amino-1,2,4-triazole, 4-(2-Aminoethyl)-pyridine and the like.
  • the polyurethane dispersant described in W097/26984, in addition to the polyisocyanate, hydroxy compound, the anchoring end group used is a Michael addition reaction product, such as an active hydrogen-containing heterocyclic compound and hydroxypropyl (ethyl) acrylate, or An addition product of an active hydrogen heterocyclic compound and a glycidyl ether.
  • the polyurethane dispersant of CN200780044910 also employs an anchoring end group which is added by Michael and is a reactant of a dinonylaminoalkylamine and a hydroxyl group-containing ⁇ , ⁇ -unsaturated carbonyl compound.
  • the polyurethane dispersant of 2007/05145 uses an unsaturated monohydroxy compound as a paving group, such as propargyl alcohol, decyl alcohol, etc., and the final product is characterized by no ammonia value.
  • the above polyurethane dispersant adopts different types of anchoring end groups, which can disperse inorganic and some organic pigments well, but for some organic pigments, especially phthalocyanines, isoporphyrins, carbon black, etc. There is a disadvantage that the coloring power of the dispersion is not strong and the storage stability of the color paste is insufficient.
  • An object of the present invention is to provide a novel polyurethane dispersant and a process for the preparation thereof, which solve the problems of the above-mentioned prior art dispersant.
  • the specific plan is as follows:
  • a novel polyurethane compound which is synthesized by a nitrogen-containing heterocyclic compound which is dehydrated and condensed with a compound containing a primary amine and a secondary amine or a hydroxyl group or a mercapto group.
  • the condensed product that is, the nitrogen-containing heterocyclic compound, contains an active hydrogen; the structural formula of the compound containing a primary amine and a secondary amine or a hydroxyl group or a thiol group is as follows:
  • n 1 to 5, preferably 2 to 4, and R 1 and R 2 are respectively a hospital base having 1 to 8 carbons, either independently or connected by a chemical bond to form one or more saturated or unsaturated 4 ⁇ 8-membered ring, X is N, 0 or S.
  • the preparation method of the above novel polyurethane compound comprises the following steps: First, in a mixed solution of xylene and butyl acetate, under the catalysis of DBTDL (dibutyltin dilaurate), component A and component B are at 70 to 80 ° C. In the middle reaction, the -NCO group in 1 to 95% of component A is blocked with component B; then, component C is added, and the reaction is continued at 70 to 80 ° C, and component C is blocked by 5 to 80%. The -NCO group in A, and the total amount of -NCO of component A blocked by component B and component C is 30 to 90%; finally, it is kept at 60 ° C for 1 hour, and is blocked with component D. -NCO remaining in component A; wherein
  • Component A is one or more isocyanate polymers having an average functionality of from 2.0 to 6.0;
  • Component B is a monohydric hydroxy compound of a polyether or polyester or polyacrylate;
  • component C is a two-functional chain extender;
  • Component D is a nitrogen-containing heterocyclic compound.
  • the component A ie, the isocyanate polymer
  • a pentamer of the diisocyanate TDI cyclization reaction (trade name Desmodur ID:
  • polyisocyanate polymers have an average functionality of 2.0 to 6.0, and suitable polymers can be purchased from Bayer, Germany or Sapici, Italy.
  • Component B of the present invention may be any monohydric hydroxy compound of the prior art, preferably polyether, polyester and polyacrylate monol.
  • component B blocks from 1 to 90% of the -NCO groups in the component, preferably from 15 to 60% of the -NCO groups in component A.
  • the monohydric hydroxy compound of the above polyester can pass through small molecule monohydric alcohols and lactones.
  • a ring opening reaction is obtained.
  • the small molecule monohydric alcohol may be any of the prior art alcohols having 4 to 30 carbon atoms, preferably 4 to 18 carbons, such as butanol, pentanol, octanol, cyclohexanol, oleyl alcohol, propargyl Alcohol, etc.
  • the lactone may be beta-propiolactone, valerolactone, caprolactone and derivatives thereof.
  • the polymerization of the lactone and the monohydric alcohol can be carried out by a known process, for example, by using a p-toluenesulfonic acid or a dibutyltin dilaurate or a tetrabutoxyzirconium as a catalyst ring-opening reaction at 100 to 180 °C.
  • a p-toluenesulfonic acid or a dibutyltin dilaurate or a tetrabutoxyzirconium as a catalyst ring-opening reaction at 100 to 180 °C.
  • the ring-opening reaction equation for small molecule monohydric alcohol and caprolactone is as follows:
  • the polyester monool can also be formed by polycondensation of a small molecule monohydric alcohol with a dihydric alcohol, a dibasic acid or an acid anhydride, or by polycondensation of a small molecule monohydric alcohol with a hydroxy acid, or a mixture of the two methods.
  • the polyester monool has a number average molecular weight of from 300 to 5,000, and a preferred molecular weight range of from 1,000 to 3,000.
  • the monohydric hydroxy compound of the above polyether that is, the polyether monol is preferably a fluorenyl-terminated poly(C 2 _4 epoxyalkyl) monool, which can be polymerized by a small molecule monohydric alcohol and a C 2 -4 epoxyalkyl monomer. And got it.
  • the small molecule monohydric alcohol contains 1 to 30 carbons, preferably 1 to 10 carbons, most preferably 1 to 4 carbons, and may be methanol, ethanol, propanol, butanol, 1-pentanol, 1-hexanol, 1-octanol, lauryl alcohol, benzyl alcohol, methyl phenol, nonyl phenol, dodecyl phenol, and the like.
  • the fluorenyl moiety of the C 2 _4 epoxy fluorenyl group may be linear or contain a branch such as ethylene epoxide, propylene oxime, butyl oxime, tetrahydrofuran or a copolymer thereof.
  • the polyether monool has a number average molecular weight of from 300 to 6,000, and a preferred molecular weight range of from 1,000 to 4,000.
  • the polyacrylate monool has a number average molecular weight of 300 to 20,000, and a preferred molecular weight range is 500 to 10,000.
  • the monohydric hydroxy compound of the polyether is preferably a fluorenyl-terminated poly(C 2 -4 epoxyfluorenyl) monohydric alcohol which can be subjected to ring-opening polymerization of a small molecule monohydric alcohol or a monocarboxylic acid and an epoxy fluorenyl monomer. And got it.
  • the monovalent hydroxy compound of the polyacrylate is composed of a (meth) acrylate monomer
  • R is an alkyl group having 1 to 18 carbons, preferably 1 to 12 carbons, and most preferably 1 to 4 carbons.
  • the difunctional chain extender, component C is a diol, a diamine or a dicarboxylic acid having a number average molecular weight of 600 to 2000, preferably a polydecyloxy diol, a polyester binary An alcohol, wherein the polyalkoxy diol has a decyloxy carbon content of 24, and may be polyethylene glycol, polypropylene glycol, polytetrahydrofuran diol, polybutene diol, preferably polyethylene glycol, polypropylene glycol And their mixed diols.
  • Component C blocks 5 to 80% of the -NCO group in component A, and a more suitable ratio is 15 to 30%.
  • the appropriate ratio of B and C to block the total amount of -NCO in component A is 30 to 90%.
  • the preparation method of the nitrogen-containing heterocyclic compound is as follows:
  • An acid anhydride having a molar ratio of 1:1 is dehydrated and condensed with a compound containing a primary amine and a secondary amine or a hydroxyl group or a thiol group at 180 to 230 ° C, and the condensed product, that is, the nitrogen-containing heterocyclic compound contains An active hydrogen;
  • the structural formula of the compound containing a primary amine and a secondary amine or a hydroxyl group or a thiol group is as follows -
  • n 1 to 5, preferably 2 to 4, and R 1 and R 2 are respectively a fluorenyl group having 1 to 8 carbons, either independently or connected by a chemical bond to form one or more saturated or unsaturated 4 ⁇ 8-membered ring, X is N, 0 or S.
  • the acid anhydride is selected from the group consisting of phthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, chlorophthalic anhydride, brominated phthalic anhydride, fluorophthalic acid phthalate, methyl phthalic acid Formic anhydride, naphthalic anhydride or 2,3 naphthalene dicarboxylic anhydride.
  • the nitrogen-containing heterocyclic compound is 3-(2-aminoethyl)anthracene, 4-(2-aminoethyl)benzyl alcohol, 1 H-imidazoleethylamine, 4-hydroxyphenylethylamine, 2-(2) -aminoethyl)phenol, 2-methylindole-3-ethylamine, N-ethylethylenediamine, N-phenylethylenediamine, 3-(aminomethyl)pyridinium, 2-(aminocarba Morpholine, 5-(aminomethyl)indole, 4-(aminomethyl)benzyl alcohol, 5-aminomethylcarbazole, 2-(2-aminopropyl)pyrrole, 4-(2-amino Propyl) phenol, 1-(2-aminoethyl)piperazine, 4-methyl-5-aminopurine, 5-aminoisoindoline, 1-amino 4-hydroxyindole, 4-aminobenzimidazole, 4-a
  • such a heterocyclic compound is 4-aminobenzimidazole, 3-(2-aminoethyl)anthracene, 2-(aminomethyl)morpholine, 1-(2-aminoethyl)piperazine, etc. .
  • it has the following structural formula:
  • the polycondensation reaction for preparing component D can be carried out by a known method reported in the literature.
  • the preferred process is: adding an acid anhydride and a heterocyclic compound according to a certain molar ratio, dehydrating between 180 and 230 ° C to complete the reaction, and finally diluting with a mixture of one or more polar solvents, such as isobutanol, propylene glycol Methyl ether, cyclohexanone, hydrazine/hydrazine, hydrazine, gave component D of the present invention.
  • polar solvents such as isobutanol, propylene glycol Methyl ether, cyclohexanone, hydrazine/hydrazine, hydrazine
  • the polyurethane dispersant of the invention is mainly used for the dispersion of pigments and fillers in coatings and inks, and the pigments and fillers used in any coatings and inks are suitable.
  • metal oxide pigments such as titanium dioxide, iron oxide of various colors, zinc oxide, fillers such as talc, kaolin, silica, barite, various organic pigments such as benzimidazolone, azo, quinacridine Ketones, actinides, anthraquinones, isoporphyrins, DPPs, etc., and carbon black.
  • the dispersant of the present invention is based on the special structure of the self-supporting anchoring end group, it has a very good effect on the dispersion and stabilization of high-performance organic pigments such as azo, isoporphyrin and carbon black, and overcomes the conventional polyurethane.
  • the dispersing agent has a disadvantage that the coloring power which is present when the pigment is dispersed is not strong, and the storage stability of the color paste is poor.
  • Figure 1 is an infrared spectrum of the product of Example 2;
  • Figure 2 is a GPC spectrum of the product of Example 1.
  • the hydroxyl value is 35 and the number average molecular weight is 1600.
  • 1,4-butanediol 11.20 parts, 0.124 mol
  • ⁇ -caprolactone 77.22 parts, 0.677 mol
  • ⁇ -valerolactone 11.58 parts, 0.116 mol
  • the dispersant of polyurethane was prepared in the same manner as in Comparative Example 1, except that Desmodur IL (19.02 parts), polyester monol B1 (23.38 parts), diol C1 (1.55 parts), anchor end group D2 ( 11.10 parts) Instead of the corresponding components therein, a pale yellow transparent liquid having a viscosity of 40% of a solid was obtained, and the ammonia value was 3.2.
  • Figure 1 shows the infrared spectrum of the product
  • Figure 2 shows the GPC spectrum of the product. The analysis results are shown in Table 1 below:
  • the polyurethane dispersant was prepared in the same manner as in Comparative Example 1, except that Desmodur IL (17.81 parts), polyester monol B1 (23.75 parts), PEG 2000 (2.23 parts), and anchor end group D1 (10.39 parts) were used. Instead of the components therein, a pale yellow transparent liquid having a viscosity of 40% of a solid was obtained, and the ammonia value was 5.8.
  • the polyurethane dispersant was prepared in the same manner as in Comparative Example 1, except that Desmodur IL (19.66 parts), polyester monol B2 (22.33 parts), PEG 2000 (2.21 parts), and anchor end groups D3 (11.14 parts) were used. Instead of the components therein, a pale yellow transparent liquid having a viscosity of 40% solid was obtained, and the ammonia value was 12.5.
  • Desmodur IL (19.66 parts), polyester monol B2 (22.33 parts), PEG 2000 (2.21 parts), and anchor end groups D3 (11.14 parts) were used. Instead of the components therein, a pale yellow transparent liquid having a viscosity of 40% solid was obtained, and the ammonia value was 12.5.
  • the polyurethane dispersant was prepared in the same manner as in Comparative Example 1, except that Desmodur lL (20.78 parts), polyacrylate monol B3 (21.76 parts), PEG 2000 (1.39 parts), and anchor end group D2 (12.12 parts) were used. Instead of the components therein, a pale yellow transparent liquid having a viscosity of 40% of a solid was obtained, and the ammonia value was 3.5.
  • the polyurethane dispersant was prepared in the same manner as in Comparative Example 2, except that Desmodur N (11.92 parts), polyester monol B2 (27.74 parts), PEG 1000 (153 parts), and anchor end group D3 (13.62 parts) were used. Instead of the components therein, a pale yellow transparent liquid having a solid fraction of 45% was obtained with an ammonia value of 4.8.
  • the polyurethane dispersant was prepared in the same manner as in Comparative Example 2 except that Desmodur N (13.23 parts), polyether monol B5 (25.21 parts), PEG 2000 (3.53 parts), and anchor end group D1 (12.0 parts) were used. Instead of the components therein, a pale yellow transparent liquid having a solids content of 45% was obtained with an ammonia value of 13.3.
  • the polyurethane dispersant was prepared in the same manner as in Comparative Example 2, except that Desmodur HL (15.35 parts, 60 ° / butyl acetate solution, Bayer products), polyester monol B1 (23.37 parts), PEG 800 were used. (1.34 parts), anchoring terminal group D2 (12.02 parts) and replacing the components therein, a pale yellow transparent liquid having a solid content of 40% was obtained, and the ammonia value was 3.8.
  • the polyurethane dispersant was prepared in the same manner as in Comparative Example 2, except that Desmodur HL (13.72 parts), polyether monol B4 (25.03 parts), diol C2 (1.34 parts), and anchor end group D3 (10.37) were respectively used. In lieu of the components, a pale yellow transparent liquid having a solids content of 40% was obtained with an ammonia value of 4.5.
  • Example 6 1 1 1 1 8.9 1
  • Example 7 1 1 1 1 1 1 8.9 Pigment Yellow 110 15 15 15 1 1 /
  • Table 2 is a pigment slurry formulation containing the polyurethane dispersant of the present invention and a comparative dispersant, respectively.
  • the preparation process is as follows: In a shock bottle The dispersant, 1: 1 xylene and propylene glycol methyl ether acetate mixed solvent, pigment, and resin were sequentially added and stirred uniformly. Finally, a certain amount of glass beads (2 to 3 mm in diameter) was placed and dispersed in a shaker for 2 hours. After cooling, a pigment slurry is obtained.
  • Table 3 is the viscosity of the pigment award in Table 2 and the thermal stability test data in 5CTC, as follows: Viscosity of the pigment paste and thermal stability test data
  • the pigment syrups I to VI were prepared according to the ratio of the hydroxy acrylic resin: pigment syrup: curing agent: mixed solvent in a molar ratio of 5:3:2.5:1.5, and the preparation process was as follows: hydroxy acrylic resin After mixing with the pigment slurry, it was dispersed by a high speed mixer (5000 rpm * 3 min). After the dispersion was completed, the solvent and the curing agent were added and stirred by hand. After the above color paint was filtered, it was scraped on a polyester sheet with a 60 ⁇ m wire bar and dried at room temperature.
  • the 20 degree gloss data of the test polyester film is as follows:
  • the polyurethane dispersant of the present invention has obvious adsorption capacity for the pigment due to the use of a novel anchoring end group based on the conventional anchoring end group-based polyurethane dispersing agent.
  • the viscosity of the pigment paste (11, III, V, VI) is significantly reduced, and the thermal stability of the pigment slurry after storage in 5 CTC is greatly improved.
  • the dispersant can better stabilize the pigment particles which are unraveled during the grinding process, and better overcome the re-aggregation caused by the London van der Waals force between the pigment particles. Phenomenon, thus the pigment can be dispersed to a smaller particle size. Therefore, the 20 degree gloss data of the color paint based on the polyurethane dispersant of the present invention is better, and the pigment coloring power is more fully embodied.

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Abstract

一种聚氨酯分散剂及其制备方法，所述聚氨酯分散剂在合成时由含氮杂环化合物封端，所述含氮杂环化合物由酸酐与含一个伯胺和一个仲胺或羟基或巯基的化合物脱水缩合而成，所述缩合后的产物即所述含氮杂环化合物，含有一个活泼氢；所述含一个伯胺和一个仲胺或羟基或巯基的化合物的结构式如式（I）所示。其中n=1〜5，优选2〜4，R1和R2分别为含1〜8个碳的烷基，两者或独立，或通过化学键相连形成一个或几个饱和或不饱和的4〜8元环，X为N、O或S。

Description

一种聚氨酯分散剂及其制备方法 技术领域
本发明涉及一种聚氨酯型分散剂及其制备方法，该分散剂用异氰酸酯多聚体 与羟基化合物反应后，最后用自制的新型锚定端基封端。本发明进一步阐述了这 种新型锚定端基的制备方法， 以及在聚氨酯分散剂中的应用。
背景技术
在液体介质中引入固体颗粒需要强大的机械力，而且，这些固体颗粒分散于 液体介质后， 由于固体颗粒之间的伦敦力 /范德华力引起相互吸引， 进而重新聚 集，破坏了分散体的稳定， 导致先前所做的努力白费。 因此， 通常通过引入分散 剂的方法来改善固体颗粒进入液体介质中的效率和提高分散体的稳定性。
分散剂是一种在分子内同时具有亲油性和亲水性两种相反性质的界面活性 剂，其结构的一部分带有极性较大的锚定端基，容易吸附在固体颗粒的表面， 另 一部分则是极性较低的溶剂化长分子链， 与分散介质 (树脂或溶剂)有较好的亲和 力。 因此， 分散剂可均一分散那些难溶于液体的无机、有机颜料的固体颗粒， 同 时也能防止固体颗粒的沉降和凝聚， 形成较稳定的悬浮液。
随着有机颜料和碳黑在涂料、油墨以及塑料中的广泛使用，想彻底改善这些 颜料在液体中的稳定性，高分子量分散剂成为一种必不可少的添加物，譬如聚丙 烯酸酯类、聚氨酯类分散剂等。而其中， 聚氨酯类分散剂由于其所具有的特殊聚 异氰酸酯核， 以及其 NCO的高反应活性， 能和不同极性的一元醇尾段反应生成 位阻链段，因此很容易能得到对有机颜料的稳定性较强，与体系相容性广泛的高 分子量分散剂， 使得许多高性能的有机颜料的分散稳定不再成为问题。
US4032698提到了一种聚氨酯类分散剂， 采用 2.5-6个官能度的多异氰酸 酯、聚丙烯酸酯一元醇以及锚定端基制备而成，锚定端基为含 -SH或 -OH或 -NH2 等反应性基团的碱性反应物， 譬如双氰胺、 二硝基苯胺、 二氨基马来腈、 3-氨基 -1、 2、 3-三唑等。
EP154678提到了一种聚氨酯类分散剂，采用多异氰酸酯、羟基化合物以及 一种含泽尼维季诺夫 (zerewitinoff)活泼氢和至少一个含氮的碱性基团的化合物 制备而成。 其中作为锚定端基的这种含活泼氢化合物优先采用含 -NH( 的杂环化 合物， 譬如 1-(2-氨乙基)哌嗪， 3-氨基 -1 ,2,4-三唑， 4-(2-氨乙基) -吡啶等等。 W097/26984所述的聚氨酯分散剂， 除了多异氰酸酯、 羟基化合物外， 所 用的锚定端基为 Michael加成反应产物，如含活泼氢的杂环化合物与丙烯酸羟丙 (乙)酯， 或者含活泼氢杂环化合物与缩水甘油醚的加成产物。
CN200780044910中的聚氨酯分散剂同样采用了由 Michael加成而得的锚 定端基， 为二垸基胺基烷基胺与含羟基官能团的 α,β-不饱和羰基化合物的反应 物。
ΕΡ2007/05145的聚氨酯分散剂采用了不饱和的单羟基化合物做铺定基团， 譬如炔丙醇、 糠醇等， 最终的产物特征是没有氨值。
上述的聚氨酯分散剂采用了不同类型的锚定端基，能较好地分散无机和部分 有机颜料， 但对于某些有机颜料， 尤其是酞菁类、异吲哚啉类、碳黑等， 均存在 分散体着色力不强， 色浆贮存稳定性不足的缺点。
发明内容
本发明的目的在于提供一种新型聚氨酯分散剂及其制备方法，解决上述现有 分散剂存在的问题。 具体方案如下：
一种新型聚氨酯化合物， 所述聚氨酯化合物在合成时由含氮杂环化合物封 端，所述含氮杂环化合物由酸酐与含一个伯胺和一个仲胺或羟基或巯基的化合物 脱水缩合而成， 所述缩合后的产物即所述含氮杂环化合物含有一个活泼氢； 所述含一个伯胺和一个仲胺或羟基或巯基的化合物的结构式如下：
Η2Ν― (CH2)n― R- XH一 R2
、、、、 '
其中 n=1〜5, 优选 2〜4, R1和 R2分别为含 1〜8个碳的院基， 两者或独立， 或通过化学键相连形成一个或几个饱和或不饱和的 4〜8元环， X为 N、 0或 S。
上述新型聚氨酯化合物的制备方法，包括如下步骤： 首先，在二甲苯和醋酸 丁酯混合溶液中， DBTDL (二月桂酸二丁基锡）催化作用下， 组分 A和组分 B 在 70〜80°C中反应， 用组分 B封闭掉 1〜95%组分 A中的 -NCO基团； 然后， 投入组分 C，继续在 70〜80°C下反应，组分 C封闭掉 5〜80%组分 A中的 -NCO 基团， 并且， 组分 B和组分 C封闭的组分 A的- NCO总量为 30〜90%； 最后， 60°C下保温 1小时， 用组分 D封闭掉组分 A中剩余的 -NCO; 其中，
组分 A为一种或多种含 2.0到 6.0平均官能度的异氰酸酯多聚体； 组分 B为聚醚或聚酯或聚丙烯酸酯的一元羟基化合物； 组分 C为两官能度的扩链剂；
组分 D为含氮杂环化合物。
具体地， 举例来说， 所述组分 A即异氰酸酯多聚体是己二异氰酸酯（HDI)、 甲苯二异氰酸酯（TDI)、 异佛尔酮二异氰酸酯（IPDI )、 4,4'-二苯基甲垸-二异氰 酸酯 （MDI )、 苯二亚甲基二异氰酸酯 （XDI )、 4,4-二环己基甲烷二异氰酸酯 (H12MDI)、 丁二异氰酸酯 （BDI)、 辛二异氰酸酯 （ODI)等二异氰酸酯的加成 物，优选 HDI、 TDI、 IPDI以及 XDI。譬如二异氰酸酯 TDI环化反应的五聚体（商 品名称 Desmodur ID:
Figure imgf000004_0001
IPDI和 TDI的环化自聚体：
Figure imgf000004_0002
这些多异氰酸酯多聚体具有 2.0到 6.0平均官能度， 合适的多聚体均可购自 德国 Bayer公司或者意大利 Sapici公司。
本发明所述的组分 B可以是现有技术中任何的一元羟基化合物， 优选的是 聚醚、 聚酯和聚丙烯酸酯一元醇。
一般地， 组分 B封闭掉组分 中 1〜90%的 -NCO基团， 优选地， 是封闭组 分 A中 15〜60%的 -NCO基团。
上述聚酯的一元羟基化合物即聚酯一元醇可以通过小分子一元醇与内酯的 开环反应得到。 小分子一元醇可以是含 4〜30个碳原子的现有技术中的任何一 种醇， 优选 4〜18个碳， 譬如丁醇、 戊醇、 辛醇、 环己醇、 油醇、 炔丙醇等。 内酯可以是 β-丙内酯、 戊内酯、 己内酯以及它们的衍生物。 内酯与一元醇的聚 合可以通过已知的工艺进行， 例如在 100〜180°C下用对甲苯磺酸或者二丁基二 月桂酸锡、四丁氧基锆做催化剂开环反应而得。譬如小分子一元醇与己内酯的开 环反应反应方程式如下：
Figure imgf000005_0001
聚酯一元醇也可以通过小分子一元醇与二元醇、 二元酸、酸酐縮聚而成， 还 可以通过小分子一元醇与羟基酸縮聚而成， 或者是这两种方法的混合。
聚酯一元醇的数均分子量为 300〜5000，优选的分子量范围是 1000〜3000。 上述聚醚的一元羟基化合物即聚醚一元醇优选为垸基端基的聚 (C2_4环氧烷 基)一元醇， 它可以通过小分子一元醇与 C2_4环氧烷基单体聚合而得。 其中小分 子一元醇含 1〜30个碳， 优选是 1〜10个碳， 最优选 1〜4个碳， 可以是甲醇、 乙醇、 丙醇、 丁醇、 1-戊醇、 1-己醇、 1-辛醇、 月桂醇、 苯甲醇、 甲基苯酚、 壬 基酚、 十二垸基苯酚等。 C2_4环氧垸基基团的垸基部分可以是线性或含有支链， 如环氧乙垸、 环氧丙垸、 环氧丁垸、 四氢呋喃或者它们的共聚物。
聚醚一元醇的数均分子量为 300〜6000，优选的分子量范围是 1000〜4000。 聚丙烯酸酯一元醇是基于聚 (甲基)丙烯酸酯聚合物的一个尾端为羟基的聚 合物。 这种聚合物可以通过 (甲基)丙烯酸酯单体 CH2=C(CH3)C(=0)OR在 2-巯 基乙醇的调聚作用下， 用常规引发剂（如 AIBN)制备而成。 其中的 R可以是含 1〜18个碳的烷基， 优选的是 1〜12个碳， 最优选的是 1〜4个碳。 聚丙烯酸酯 一元醇
Figure imgf000005_0002
聚丙烯酸酯一元醇的数均分子量为 300〜20000， 优选的分子量范围是 500〜 10000。 所述聚醚的一元羟基化合物优选为垸基端基的聚 (C2-4环氧垸基)一元醇， 它 可以通过小分子一元醇或者一元羧酸与 环氧垸基单体开环聚合而得。
所述聚丙烯酸酯的一元羟基化合物由（甲基）丙烯酸酯单体
CH2=C(CH3)C(=0)OR在 2-巯基乙醇的调聚作用下， 用常规引发剂制备而成， 数均分子量为 300〜20000， 优选的是 500〜10000。其中 R是含 1〜18个碳的 烷基， 优选的是 1〜12个碳， 最优选的是 1〜4个碳。
所述两官能度的扩链剂即组分 C是数均分子量为 600〜2000的二元醇、 二 元胺或二元羧酸， 优选的是聚垸氧基二元醇、聚酯二元醇， 其中聚烷氧基二元醇 的垸氧基含碳为 24， 可以是聚乙二醇、 聚丙二醇、 聚四氢呋喃二醇、 聚丁烯二 醇， 优选的是聚乙二醇、 聚丙二醇及它们的混合二元醇。 组分 C封闭掉组分 A 中 5〜80%的 -NCO基团， 更合适的比例是 15〜30%。 B和 C封闭掉组分 A中 -NCO总量的合适比例在 30〜90%。
所述含氮杂环化合物的制备方法如下：
由摩尔比 1 : 1 的酸酐与含一个伯胺和一个仲胺或羟基或巯基的化合物在 180〜230'C下脱水縮合而成， 所述縮合后的产物即所述含氮杂环化合物含有一 个活泼氢；
所述含一个伯胺和一个仲胺或羟基或巯基的化合物的结构式如下-
H2N― (CH2)n― R- XH― R2
、、、、
、、 /
其中 n=1〜5， 优选 2〜4， R1和 R2分别为含 1〜8个碳的垸基， 两者或独立， 或通过化学键相连形成一个或几个饱和或不饱和的 4〜8元环， X为 N、 0或 S。
所述酸酐选自邻苯二甲酸酐、四氢苯酐、甲基四氢苯酐、氯代邻苯二甲酸酐、 溴代邻苯二甲酸酐、氟代邻苯二甲酸酑、 甲基邻苯二甲酸酐、萘酐或 2，3萘二羧 酸酐等。
所述含氮杂环化合物是 3-(2-氨乙基)吲哚、 4-(2-氨基乙基)苯甲醇、 1 H-咪唑 乙胺、 4-羟基苯乙胺、 2-(2-氨基乙基)苯酚、 2-甲基吲哚 -3-乙胺、 N-乙基乙二 胺、 N-苯基乙二胺、 3- (氨基甲基)吡挫、 2- (氨基甲基)吗啉、 5- (氨基甲基)吲哚、 4- (氨基甲基)苄醇、 5-氨基甲基吲唑、 2-(2-氨基丙基)吡咯、 4-(2-氨基丙基)苯酚、 1-(2-氨乙基)哌嗪、 4-甲基 -5-氨基吲哚、 5-氨基异吲哚啉、 1-氨基 4-羟基蒽醌、 4-氨基苯并咪唑、 4-氨基 -3-巯基吡啶、 2-巯基苯并咪唑或 2-(2-氨基乙基)苯鼢等。 优选地， 此类杂环化合物是 4-氨基苯并咪唑、 3-(2-氨乙基)吲哚、 2- (氨基甲 基)吗啉、 1-(2-氨乙基)哌嗪等。 例如， 具有如下结构式：
Figure imgf000007_0001
制备组分 D的缩聚反应可以采用文献报道的已知方法。 优选的工艺是： 按 照一定的摩尔比投入酸酐和杂环化合物， 在 180〜230'C之间脱水完成反应， 最 后用一种或几种极性溶剂的混合物兑稀， 譬如异丁醇、 丙二醇甲醚、 环己酮、 Λ/ΠΒΚ、 ΝΜΡ, 得到本发明所述的组分 D。
组分 D的一种可能的结构式是：
苯酑和 3-(2-氨乙基)吲哚反应的脱水缩合物 2-((3-吲哚)乙基)异吲哚 -1 ,3-二 酮：
Figure imgf000007_0002
组分 D的另一种可能的结构式是：
苯酐和 1-(2-氨乙基)哌嗪反应的脱水缩合物 2-((1-哌嗪)乙基)异吲哚 -1 ,3-
Figure imgf000007_0003
本发明所述的聚氨酯分散剂主要用于涂料和油墨中颜、填料的分散，任何涂 料和油墨中使用的颜填料均适用。譬如金属氧化物颜料如二氧化钛、各种颜色的 氧化铁、 氧化锌， 填料如滑石、 高岭土、二氧化硅、 重晶石， 各种有机颜料如苯 并咪唑酮类、 偶氮类、 喹吖啶酮类、 茈系、 蒽醌类、 异吲哚啉系、 DPP 系等以 及碳黑。 由于本发明所述分散剂基于自制锚定端基的特殊结构， 因此对偶氮类、异吲 哚啉系以及碳黑等高性能有机颜料的分散和稳定尤其有着非常好的效果，克服了 以往聚氨酯类分散剂在分散此类颜料时存在的着色力不强，色浆贮存稳定性差的 缺点。
附图说明
图 1是实施例 2的产物的红外光谱图；
图 2是实施例 1产物的 GPC图谱。
具体实施方式
下面，用实施例来进一步说明本发明内容，但本发明的保护范围并不仅限于 实施例。对本领域的技术人员在不背离本发明精神和保护范围的情况下做出的其 它的变化和修改， 仍包括在本发明保护范围之内。
实施例 1
组分 B的制备：
聚酯一元醇 B1 (反应物摩尔比为正辛醇： ε-己内酯 =1 : 14.65, Μη=1800): 在氮气保护下，投入正辛醇 (7.24份， 0.056mol)、 ε-己内酯 (92.76份， 0.814mol)， 搅拌下升温至 110'C， 投入二丁基二月桂酸锡 (DBTDL, 0.03份， 10%的丁醇溶 液)， 继续升温到 170〜180°C保温 6hr以上至固体分达标， 得到常温下为白色常 温蜡状固体， 羟值 32， 此为聚酯一元醇 B1 , 数均分子量 1800。
聚酯一元醇 B2(异辛醇： ε-己内酯: δ-戊内酯 =1 : 8.67： 4.94， Μη=1600): 制备工艺同聚酯一元醇 Β1的制备方法，得到透明液状物，羟值 35，数均分子量 1600。
聚丙烯酸酯一元醇 Β3(ΜΜΑ: 巯基乙醇： ΑΙΒΝ=142: 7.25： 1 , Μη=2000): 预先准备两个滴加釜， 分别装有组分 Α: 甲基丙烯酸甲酯 (57份， 0.569mol), 组 分 B: 2-巯基乙醇 (2.33份， 0.029mol)， 偶氮二异丁腈 (0.67份， 0.004mol)和醋 酸乙酯 (20份)的混合物。在氮气保护下，投入醋酸乙酯 (20份)，升温至回流温度， 开始滴加组分 A， 半小时后开始滴加组分 B， 均 200分钟滴完， 滴加结束后， 继 续在 80°C左右保温至固体分达标， 最后升温至 120'C抽真空拔出溶剂， 得到全 固份样品， 浅黄色透明， 羟值为 27.50， 数均分子量 2000。
聚醚一元醇 B4(MPEG2000， Mn=2000), B4为市售产品， 羟值 28， 常温 白色蜡状固体。 聚醚一元醇 B5(丁氧基 EO:PO=1 : 1—元醇， Mn=1000)， B5为市售产品， 羟值 56， 常温无色液体。
组分 C的制备：二元醇 C1 (反应物摩尔比为丁二醇： ε-己内酯： δ-戊内酯 =1 : 5.46： 0.94,
Figure imgf000009_0001
在氮气保护下， 投入 1,4-丁二醇 (11.20份， 0.124mol)， ε-己内酯 (77.22份， 0.677mol)， δ-戊内酯 (11.58份， 0.116mol), 搅拌下升温至 130'C， 投入四丁氧基锆 (0.3份， 30%的丁醇溶液)， 继续升温到 175-180°C保温 6hr以上至固体分达标， 得到轻微蜡状固体， 羟值 141， 数均分子量 800。
二元醇 C2(反应物摩尔比为 PEG200: ε-己内酯 =1 : 10.53， Μη=1400): 工 艺同二元醇 C1， 得到白色常温蜡状固体， 羟值 40, 数均分子量 1400。
二元醇 C3(PEG800, Mn=800): C3为市售产品，羟值 140， 常温白色蜡状 固体。
组分 D的制备：
锚定端基 D1 (反应物摩尔比为邻苯二甲酸酐： 4-氨基苯并咪唑 =1 : 1)： 在氮 气保护下，投入邻苯二甲酸酐 (52.66份， 0.356mol), 4-氨基苯并咪唑 (47.34份, 0.356mol)， 逐步升温至 180°C , 保温至酸值恒定， 继续升温到 220〜230°C， 保 温至酸值小于 1， 降低温度到 80°C， 用 NMP兑稀至 50%， 得到浅褐色液体， 此为锚定端基 D1。
锚定端基 D2(反应物摩尔比为邻苯二甲酸酐： 3-(2-氨乙基)吲哚 =1 : 1)： 工 艺同锚定端基 D1，用 3-(2-氨乙基)吲哚替代 4-氨基苯并咪挫，得到固体分为 50% 的浅褐色液体， 此为锚定端基 D2。 曰 MS显示， D1的分子量为 259.9。
锚定端基 D3(反应物摩尔比为邻苯二甲酸酐： 1-(2-氨乙基)哌嗪 =1 : 1)： 工 艺同锚定端基 D1，用 1-(2-氨乙基)哌嗪替代 4-氨基苯并咪唑,得到固体分为 50% 的浅褐色液体， 此为锚定端基 D3。
锚定端基 D4(反应物摩尔比为 2,3-萘二羧酸酐： 2- (氨基甲基)吗啉 =1 : 1)： 工艺同锚定端基 D1， 用 2- (氨基甲基)吗啉替代 4-氨基苯并咪挫， 得到固体分为 50%的浅褐色液体， 此为锚定端基 D4。
聚氨酯分散剂的制备
对比例 1 : 在氮气保护下， 投入 21.63份 Desmodur lL(51% 的醋酸丁酯溶 液， 拜耳公司产品)、 24.52份混合溶剂 (二甲苯:醋酸丁酯 =4: 1)、 24.33份聚酯 —元醇 B1和 0.1份的 DBTDL ( 10%的醋酸丁酯溶液）， 升温到 70°C， 保温至 NCO恒定后， 投入 1.7份二元醇 C1， 继续保温至 NCO恒定后， 投入 3.09份 4-(2-氨乙基)吡啶和 24.72份的丙二醇甲醚醋酸酯 （MPA) 的混合物， 60'C保温 1小时后出料。 得到固体分 40%的有一定粘度的浅黄色透明液体， 氨值 10.2。
对比例 2: 在氮气保护下， 投入 12.2份的 Desmodur N(75%的醋酸丁酯： 二甲苯 =1 : 1溶液，拜耳公司产品)、 22.65份混合溶剂 (二甲苯:醋酸丁酯 =1 : 1)、 28.75份的聚酯一元醇 B2和 0.1份的 DBTDL ( 10%的醋酸丁酯溶液）， 升温到 70°C， 保温至 -NCO的量恒定后，投入 1.57份的聚乙二醇 800(PEG 800), 继续 保温至 -NCO的量恒定后， 投入 12.2份的 3-苯并咪唑 -1-丙酸 -2-羟乙酯 (50%的 NMP溶液， 为苯并咪唑与丙烯酸羟乙酯的 Michael加成产物， 制备方法可参考 现有技术中的成熟工艺)和 22.65份 MPA的混合物， 升温到 60°C保温 1小时后 出料。 得到固体分 45%的浅黄色透明液体， 氨值 13.2。
实施例 2
聚氨酯的分散剂的制备方法同对比例 1， 不同的是， 分别用 Desmodur IL(19.02份)、聚酯一元醇 B1 (23.38份)、二元醇 C1(1.55份)、锚定端基 D2(11.10 份)代替其中的相应组分， 得到固体分 40%的有一定粘度的浅黄色透明液体， 氨 值为 3.2。 图 1为产物的红外光谱图， 图 2为该产物的 GPC图谱， 其分析结果 如下表 1所示：
Figure imgf000010_0001
实施例 3
聚氨酯分散剂的制备方法同对比例 1 ,不同的是,分别用 Desmodur IL(17.81 份)、聚酯一元醇 B1(23.75份)、 PEG 2000(2.23份)、锚定端基 D1 (10.39份）代 替其中的组分， 得到固体分 40%的有一定粘度的浅黄色透明液体， 氨值为 5.8。
实施例 4
聚氨酯分散剂的制备方法同对比例 1，不同的是，分别用 Desmodur IL(19.66 份)、 聚酯一元醇 B2(22.33份)、 PEG 2000(2.21份)、 锚定端基 D3(11.14份)代 替其中的组分，得到固体分 40%的有一定粘度的浅黄色透明液体，氨值为 12.5。 实施例 5
聚氨酯分散剂的制备方法同对比例 1，不同的是,分别用 Desmodur lL(20.78 份)、聚丙烯酸酯一元醇 B3(21.76份)、 PEG 2000 (1.39份)、锚定端基 D2(12.12 份)代替其中的组分， 得到固体分 40%的有一定粘度的浅黄色透明液体， 氨值为 3.5。
实施例 6
聚氨酯分散剂的制备方法同对比例 2，不同的是，分别用 Desmodur N(11.92 份)、 聚酯一元醇 B2(27.74份)、 PEG 1000 (153份)、 锚定端基 D3(13.62份) 替代其中的组分， 得到固体分 45%的浅黄色透明液体， 氨值为 4.8。
实施例 7
聚氨酯分散剂的制备方法同对比例 2，不同的是，分别用 Desmodur N(13.23 份)、 聚醚一元醇 B5(25.21份)、 PEG 2000 (3.53份)、 锚定端基 D1(12.0份)替 代其中的组分， 得到固体分 45%的浅黄色透明液体， 氨值 13.3。
实施例 8
聚氨酯分散剂的制备方法同对比例 2， 不同的是， 分别用 Desmodur HL(15.35份， 60°/。的醋酸丁酯溶液，拜耳公司产品)、聚酯一元醇 B1 (23.37份)、 PEG 800 (1.34份)、锚定端基 D2(12.02份)和替代其中的组分，得到固体分 40% 的浅黄色透明液体， 氨值 3.8。
实施例 9
聚氨酯分散剂的制备方法同对比例 2， 不同的是， 分别用 Desmodur HL(13.72份)、聚醚一元醇 B4(25.03份)、二元醇 C2(1.34份)、锚定端基 D3(10.37 份)替代其中的组分， 得到固体分 40%的浅黄色透明液体， 氨值 4.5。
本发明应用测试数据
为评估本发明聚氨酯分散剂的分散性能，制备了相应的颜料浆，评价其色浆 降黏及贮存稳定性能， 并将颜料浆调入到树脂中， 评价其展色能力。具体评价过 程和测试结果如下所示。
表 2本发明的颜料浆配方（重量比）
Figure imgf000011_0001
羟基丙烯酸树脂
31 31 31 30 30 30
(NV=60%)
对比例 1 15 1 1 1 1 1 实施例 2 1 15 1 1 1 1 分
实施例 4 1 1 15 1 1 1 散
对比例 2 1 1 1 8.9 1 1 剂
实施例 6 1 1 1 1 8.9 1 实施例 7 1 1 1 1 1 8.9 颜料黄 110 15 15 15 1 1 /
FW200 1 1 / 10 10 10 混合溶剂 39 39 39 51.1 51.1 51.1 合计 100 100 100 100 100 100 表 2是分别含本发明的聚氨酯分散剂与对比分散剂的颜料浆配方，制备工艺 如下： 在震荡瓶中依次投入分散剂、 1： 1 的二甲苯和丙二醇甲醚醋酸酯混合溶 剂、颜料、树脂后搅拌均匀， 最后投入一定量的玻璃珠 (直径 2〜3 mm), 放入震 荡机中分散 2小时后冷却， 即得到颜料漿。
表 3是表 2中颜料奖的粘度以及在 5CTC中热稳定性测试数据， 如下： 颜料浆的粘度以及热稳定性测试数据
Figure imgf000012_0001
* BROOKFIELD RVDV-I数显粘度计
将上述颜料浆 I〜VI按照羟基丙烯酸树脂： 颜料浆： 固化剂： 混合溶剂的摩 尔比为 5: 3： 2.5： 1.5的比例， 分别制备了色漆 I〜VI， 制备工艺如下： 羟基 丙烯酸树脂与颜料浆混合后， 用高速搅拌机分散（5000rpm*3min) ， 分散完成 后， 加入溶剂、 固化剂并手搅均匀。 上述色漆过滤后， 将其用 60ym绕丝棒刮涂 于聚酯片上， 室温干燥。 检测色漆聚酯片的 20度光泽数据如下：
表 4色漆 20度光泽数据
Figure imgf000013_0001
从上述表 3和表 4的数据可以明显看出， 对比基于传统锚定端基的聚氨酯分散 剂，本发明的聚氨酯分散剂由于采用了新型的锚定端基，对颜料的吸附能力有了 明显提高， 因而颜料浆（11、 III、 V、 VI) 的粘度有了明显的降低， 颜料浆在 5CTC中贮存后的热稳定性有了大幅改善。 同时由于锚定端基吸附能力的提高， 有助于分散剂能够更好的稳定住研磨过程中被解开的颜料颗粒，更好的克服了由 于颜料颗粒之间的伦敦范德华力引起的再聚集现象，因而颜料能被分散到更小的 粒径。 因此基于本发明之聚氨酯分散剂的色漆 20度光泽数据更好， 颜料着色力 体现的更加充分。

Claims

权 利 要 求
1、 一种新型聚氨酯分散剂， 其特征在于， 所述聚氨酯化合物在合成时由含氮杂 环化合物封端，所述含氮杂环化合物由酸酐与含一个伯胺和一个仲胺或羟基或巯 基的化合物脱水缩合而成，所述缩合后的产物即所述含氮杂环化合物含有一个活 泼氢；
所述含一个伯胺和一个仲胺或羟基或巯基的化合物的结构式如下：
H2N― (CH2)n— R- XH― R2
\ /
、、
其中 n=1〜5; R1和 R2分别为含 1〜8个碳的垸基， 虚线连接表示两者或独立， 或通过化学键相连形成一个或几个饱和或不饱和的 4〜8元环， X为 N、 0或 S。
2、 权利要求 1所述的新型聚氨酯分散剂的制备方法， 其特征在于， 包括如下步 骤： 首先， 在二甲苯和醋酸丁酯的混合溶液中， DBTDL催化作用下， 组分 A和 组分 B在 70〜80'C中反应， 用组分 B封闭掉 1〜90%组分 A中的 -NCO基团； 然后， 投入组分 C， 继续在 70〜80'C下反应， 组分 C封闭掉 5〜80%组分 A中 的 -NCO基团，并且，组分 B和组分 C封闭的组分 A的- NCO总量为 30〜90%； 最后， 50〜60°C下保温 1小时， 用组分 D封闭掉组分 A中剩余的 -NCO; 其中， 组分 A为一种或多种含 2.0到 6.0平均官能度的异氰酸酯多聚体； 组分 B为聚醚或聚酯或聚丙烯酸酯的一元羟基化合物；
组分 C为两官能度的扩链剂；
组分 D为含氮杂环化合物。
3、 根据权利要求 2所述的制备方法， 其特征在于， 所述聚酯的一元羟基化合物 可以通过小分子一元醇与内酯的开环得到， 也可以通过小分子一元醇与二元醇、 二元酸、酸酐缩聚而成，还可以通过小分子一元醇与羟基酸縮聚而成， 或者是这 两种方法的混合。
4、 根据权利要求 2所述的制备方法， 其特征在于， 所述两官能度的扩链剂是数 均分子量为 600〜2000的二元醇、 二元胺或二元羧酸。
5、 根据权利要求 3所述的制备方法， 其特征在于， 所述聚酯的一元羟基化合物 的数均分子量为 300〜5000,所述聚醚的一元羟基化合物的数均分子量为 300〜 6000。
6、 根据权利要求 5所述的制备方法， 其特征在于， 所述聚酯的一元羟基化合物 的数均分子量优选为 1000〜3000， 所述聚醚的一元羟基化合物的数均分子量优 选为 1000〜4000。
7、 根据权利要求 2所述的制备方法， 其特征在于， 所述聚丙烯酸酯的一元羟基 化合物的制备方法如下：
由 (甲基)丙烯酸酯单体 CH2=C(CH3)C(=0)OR在 2-巯基乙醇的调聚作用下， 用常规引发剂制备而成， 数均分子量为 300〜20000， 优选的是 500-10000， 其 中 R是含 1〜18个碳的垸基。
8、 根据权利要求 2所述的制备方法， 其特征在于， 所述含氮杂环化合物的制备 方法如下：
由摩尔比为 1 : 1的酸酑与含一个伯胺和一个仲胺或羟基或巯基的化合物在 180〜230'C下脱水缩合而成， 所述缩合后的产物即所述含氮杂环化合物含有一 个活泼氢；
所述含一个伯胺和一个仲胺或羟基或巯基的化合物的结构式如下：
H2N一 (CH2)n— R- XH― R2
、、、
其中 n=1〜5， R1和 R2分别为含 1〜8个碳的垸基， 两者或独立， 或通过化学键 相连形成一个或几个饱和或不饱和的 4〜8元环， X为N、 0或 S。
9、根据权利要求 8所述的制备方法，其特征在于，所述酸酐选自邻苯二甲酸酐、 四氢苯酐、 甲基四氢苯酐、氯代邻苯二甲酸酐、溴代邻苯二甲酸酐、氟代邻苯二 甲酸酐、 甲基邻苯二甲酸酐、 萘酐或 2，3萘二羧酸酐。
10、根据权利要求 8所述的制备方法，其特征在于，所述含氮杂环化合物是 3-(2- 氨乙基)吲哚、 4-(2-氨基乙基)苯甲醇、 1 H-咪 乙胺、 4-羟基苯乙胺、 2-(2-氨 基乙基)苯酚、 2-甲基吲哚 -3-乙胺、 Ν-乙基乙二胺、 Ν-苯基乙二胺、 3- (氨基甲基) 吡 、 2- (氨基甲基)吗啉、 5- (氨基甲基)吲哚、 4- (氨基甲基)苄醇、 5-氨基甲基吲 唑、 2-(2-氨基丙基)吡咯、 4-(2-氨基丙基)苯酚、 1-(2-氨乙基)哌嗪、 4-甲基 -5-氨 基吲哚、 5-氨基异吲哚啉、 1-氨基 · -羟基蒽醌、 4-氨基苯并咪唑、 4-氨基 -3-巯基 吡啶、 2-巯基苯并咪唑或 2-(2-氨基乙基)苯酚。
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